CN1117697C - Low temp. system for producing super pure nitrogen - Google Patents

Low temp. system for producing super pure nitrogen Download PDF

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Publication number
CN1117697C
CN1117697C CN98123488A CN98123488A CN1117697C CN 1117697 C CN1117697 C CN 1117697C CN 98123488 A CN98123488 A CN 98123488A CN 98123488 A CN98123488 A CN 98123488A CN 1117697 C CN1117697 C CN 1117697C
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nitrogen
ultra
hydrogen
high purity
temperature
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CN98123488A
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CN1216750A (en
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M·L·马科斯基
小T·J·伯格曼
J·K·霍维尔
小J·P·纳特沃拉
D·R·汤普森
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Praxair Technology Inc
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Praxair Technology Inc
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    • B01D53/75—Multi-step processes
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract

A process for further purification of nitrogen gas, thereby producing ultra-high purity nitrogen which is substantially free of hydrogen, oxygen and carbon monoxide, wherein the nitrogen gas is contacted with a metal-containing adsorbent at a temperature of 150 K or less.

Description

Produce the cryogenic system of nitrogen for ultra-high purity
Technical field
The present invention relates generally to the production of nitrogen for ultra-high purity, more particularly, relate to the production of the nitrogen for ultra-high purity that uses the cold operation method.
Background technology
The user of electronic industry aspect nitrogen typically needs nitrogen for ultra-high purity, and any impurity of this nitrogen for ultra-high purity for example content of oxygen, hydrogen and carbon monoxide is less than 1ppb.The concentration of these materials in the nitrogen that is obtained by conventional cryogenic air separation plant is typically in the scope of about 0.5～2ppm.Because the boiling point of oxygen is higher than nitrogen, so low-temperature distillation almost completely can be removed it.; because the boiling point of carbon monoxide and the boiling point of nitrogen are very approaching; the boiling point of hydrogen is lower again; so the most carbon monoxide that are present in the raw air that is sent to cryogenic air separation plant also are present in the nitrogen product of device, and the hydrogen concentration in the nitrogen product stream is the twice of hydrogen concentration in the raw air approximately.
After cryogenic air separation process, use conventional adsorption method to remove these impurity typically., such device is imperfect, needs large-scale contactor because carry out purifying.
A kind of replacement method of using conventional room temperature absorption method to produce nitrogen for ultra-high purity is that hydrogen and carbon monoxide are respectively at upstream initial oxidation Cheng Shui and carbonic acid gas.These oxidation productss are being removed in the molecular sieve purification device before the Cryogenic air separation then.This oxidation is carried out with catalysis method typically.The main drawback of this method for oxidation is that it needs very high temperature, and this has increased the demand of energy, thereby has increased the expense of entire method.The oxygen that another shortcoming is to remain in the product nitrogen gas stream must be removed with another kind of method, generally is to re-use an independent low-temperature distillation method, and this has further increased the expense of whole process.
Therefore, purpose of the present invention just provides a kind of improvement system that produces nitrogen for ultra-high purity.
Summary of the invention
The present invention has realized above-mentioned purpose and other purpose, and these purposes the present invention includes for being conspicuous by reading those skilled in the art disclosed herein:
Produce the cryogenic absorption method of nitrogen for ultra-high purity, this method comprises to be contacted the nitrogen that contains one or more hydrogen, oxygen or carbon monoxide impurity and produces the nitrogen for ultra-high purity that is substantially devoid of hydrogen, oxygen and carbon monoxide with metallic sorbent material under 150k or lower temperature.
Its connotation of term used herein " cryogenic absorption " refers to the absorption of carrying out under 150k or lower temperature.
Term used herein " tower " is meaning distillation tower or separation column or distillation zone or fractionation zone, that is to say contact tower or zone of action, wherein liquid and vapor phase counter current contact are to realize separating of liquid mixture, for example by vapor phase and liquid phase series installation in tower the tower tray that vertically separates or column plate on and/or on the filler member, contact, the filler member can be structured packing member and/or filler member at random.For distillation tower further is discussed, please edit chemical engineers handbook's the 5th version that issue in McGraw-Hill books company New York, the 13rd chapter, continuous distillation method referring to R.J.Perry and C.H.Chilton.A tower can comprise an overhead condenser, and vapor condensation is the phegma of tower in this condenser.
Steam and liquid contact segregation method depend on vapour pressure poor of each component.Component will be easy in the vapor phase enrichment high-vapor-pressure (volatile or lower boiling), and low-steam pressure (difficult evaporable or high boiling) component will be easy in the liquid phase enrichment.Separation method is a partial condensation, can use thus vapour mixture cooling and in vapor phase enrichment volatile constituent and so difficult volatile constituent just in the liquid phase enrichment.Rectifying or continuous still battery are exactly that the successive that vapor phase and liquid phase counter-current treatment are obtained is partly evaporated the separation method that combines with partial condensation.The counter current contact of vapor phase and liquid phase is an adiabatic, can comprise integration contact or differential contact between the two-phase.Use the rectifying principle to come the configuration of the separating technology of separating mixture usually to be called rectifying tower, distillation tower or separation column interchangeably.Low temperature fractionation is at least in part at 150k or be lower than the rectificating method that carries out under the temperature of 150k.
Its connotation of term used herein " indirect heat exchange " refers to two kinds of fluids at them to each other without any physics contact or the heat exchange that takes place under the blended situation mutually.
" top " of term tower used herein and " bottom " its connotation refer to the part of the mid point above and below that lays respectively at tower.
Term tower used herein " top " refers at the internals of tower that section of squarer on column plate or the filler for example.
Description of drawings
Fig. 1 is the flow chart of a preferred embodiment of the invention, and wherein, cryogenic absorption technology and cryogenic air separation plant combination are in aggregates.
Fig. 2 is the schema of another preferred embodiment of the present invention, and wherein, the application of cold temperature absorbing process comes the nitrogen of purifying from storage tank.
Fig. 3 is the schema by reproducing adsorbent system in the embodiment shown in Figure 2.
Embodiment
In the method for the invention, the nitrogen of one or more hydrogen, oxygen or carbon monoxide impurity that contains the ppm magnitude is at 150k or be lower than under the temperature of 150k and contact with sorbent material.Temperature preferably is not more than about 120k, and most preferably temperature is in the scope of 80-100k.Sorbent material is gone up substantially and is adsorbed whole hydrogen, oxygen and the carbon monoxide that is present in the nitrogen, and this causes obtaining the nitrogen for ultra-high purity product, and this nitrogen for ultra-high purity is substantially devoid of hydrogen, oxygen and carbon monoxide.Carry out adsorption process at low temperatures and the nitrogen that produces in the Cryognic air separation system is discharged from separation system and directly carry out purifying, and need not before adsorption step, to carry out heating steps, so just reduced process cost.The nitrogen that is kept in the storage tank also can utilize method of the present invention to carry out purifying.In this embodiment, the nitrogen of cryogenic tank is at storage temperature or approach to contact with sorbent material under the condition of storage temperature, need not to carry out preheating.Cryogenic absorption of the present invention system can use Billy with conventional high temperature service or the much smaller contactor of the needed contactor of room temperature device, has therefore reduced the investment cost of purification devices.
Table 1 has been listed at low temperatures the suitable sorbent material of the inventive method of absorption hydrogen, oxygen and carbon monoxide effectively, and these sorbent materials comprise the sorbent material that contains nickel, copper, palladium or iron.Preferred sorbent material is nickeliferous sorbent material, and most preferred sorbent material is the oxide compound of the nickel (II) on the alumina supporter.Sorbent material preferably is loaded in the container for the suitable capacity of the sorbent material of aequum with the form of adsorbent bed.
In a preferred embodiment of the invention, sorbent material by in the atmosphere of hydrogen and nitrogen for ultra-high purity in temperature greater than 120 ℃, be preferably more than under 200 ℃ the condition and heat and regenerated.Being used for the volumeter of the most preferred composition of atmosphere of adsorbent reactivation by the nitrogen for ultra-high purity total mixture, is 1% hydrogen approximately.Hydrogen is at surface and carbon monoxide and oxygen reaction formation respectively methane and the water of sorbent material.Methane and water more faintly with the sorbent material bonding, therefore can utilize nitrogen gas stream to remove at an easy rate from adsorbent surface.Regeneration is to carry out with the different timed intervals, and this depends on the capacity and hydrogen, carbon monoxide and/or the oxygen concentration in being used as the nitrogen of present method raw material of absorbent container.When using one or more containers to produce nitrogen for ultra-high purity, can use multiple container in typical case and make one or more container regeneration.
Fig. 1 is a schema, this flowcharting the present invention and the incorporate cryogenic absorption nitrogen purification of cryogenic air separation plant system.With reference to Fig. 1, the raw air in the pipeline 1 is compressed in compressor 2, and carbonic acid gas, water and some hydrocarbon are removed by prepurifier 3.The hydrogen and the carbon monoxide that are present in the raw air can not be removed by prepurifier, because under compressor discharge condition, they can be not adsorbed by the molecular screen material of prepurifier.Purified air stream in the pipeline 4 utilizes then to rely on the indirect heat exchange that refluxes in heat exchanger 5 and is cooled to low temperature.Cold air flow in the pipeline 6 is sent into low-temperature fractionating tower 7, and raw air is separated into nitrogen and oxygen enriched liquid by low temperature fractionation in this rectifying tower.Nitrogen has quite low oxygen concn, in typical case less than 1ppm.Shown still-process is to represent the general distillation method that can produce the nitrogen with low concentration oxygen.Distillation method itself does not influence the design and the configuration of purifier.Therefore, combine, can use any method to produce nitrogen, as long as this method can deoxygenation arrive very low content with the present invention.If with a method of not producing nitrogen at low temperatures, before carrying out method of the present invention, carry out the cooling of product stream.Nitrogen for ultra-high purity can return the top that adds distillation tower, improving distillation efficiency, thereby has reduced oxygen level in the nitrogen that distillation tower produces.
Low temperature nitrogen leaves still-process, arrives low temperature purifier 12 or oxygen analyzer 10 by pipeline 8, bypass tube 9 and by-pass valve V1, before entering low temperature purifier, measures the oxygen level of low temperature nitrogen in oxygen analyzer, in case block content is uprushed.Another part nitrogen 30 enters evaporator overhead condenser 31, and in this condenser, the nitrogen condensation is returned tower 7 as backflow.Oxygen enriched liquid enters evaporator overhead condenser 31 from the bottom of tower 7 with liquid stream 33, in this condenser, is evaporated by the indirect heat exchange of carrying out with above-mentioned condensation nitrogen, and this moment, oxygen rich gas was removed from device with refuse air-flow 34.
Fig. 1 shows low temperature purifier 12.Below the functional overview of valve (V1-V18): the control valve of V1 bypass 9.V2 auxiliary liq pipeline 21.The blow-off valve of V3 pipeline 11.The valve of V4 auxiliary line 21.V5 discharges the valve of purified nitrogen product from purifier.V6 pipeline 9 or 13 cleaning valve.V7 is used for the segregaion valve with the isolated bed of reprocessing cycle product stream 12A.V8 is used for the segregaion valve with the isolated bed of reprocessing cycle product stream 12A.V9 is used for the regeneration emptying of a 12A.V10 is 22 product valve from bed 12A to pipeline.V11 is used for the segregaion valve with the isolated bed of reprocessing cycle product stream 12B.V12 is used for the segregaion valve with the isolated bed of reprocessing cycle product stream 12B.V13 is used for the regeneration emptying of a 12B.V14 bed 12B is to the product valve of pipeline 22.V15 provides the reprocessing cycle valve of product stream 14 to purifier.V16 provides pure hydrogen and product to flow 15 blended reprocessing cycle valves.V17 bed 12A regenerated valve.V18 bed 12B regenerated valve.
Use two oxygen analyzer replicate analysis.Nitrogen vapor stream enters low temperature purifier 12 by pipeline 11, in purifier 12, removes with 1ppb or is lower than the concentration of 1ppb and the hydrogen, carbon monoxide and any remaining oxygen that exist.Valve V3 is the blow-off valve of pipeline 11.Leave purifier and straight product logistics in pipeline 13 is heated to room temperature in heat exchanger 5, reclaimed then.Valve V6 is the cleaning valve of pipeline 9 or 13.
Purifier 12 of the present invention comprises two bed 12A and 12B, two beds contain metallic sorbent material, the alumina adsorption agent material that for example contains 5% balance nickel at least, preferably contain 10-30% balance nickel alumina adsorption agent material, most preferably contain 20% balance nickel alumina adsorption agent material.Purified product is from bed 12A or from bed 12B.On each purifier bed a pair of segregaion valve is arranged, its effect is that the liquid stream that purifier bed and pipeline 11 or pipeline 21 are carried is separated so that regenerate or possible parking.12A uses segregaion valve V7 and V8; 12B uses segregaion valve V11 and V12.When a bed 12B absorption, then bed 12A regeneration.
Realize that regeneration is that about 5% nitrogen for ultra-high purity product from pipeline 14 and valve 15 is mixed with the hydrogen that passes through valves 16 and pipeline 15 from groove 27, the mixture that contains about 1% (volume) hydrogen with generation, this mixture is heated to above 120 ℃ temperature in well heater 16, preferably be heated at least 200 ℃ temperature.In typical case, before the mixture of 1% hydrogen is introduced, earlier will the regenerated bed be heated at least 120 ℃ temperature.Hot-fluid is delivered to purifier bed 12A through pipeline 17 and valve V17, or delivers to 12B through valve V18, and heating adsorbent bed separately discharges any material that is adsorbed.The useless stream of regeneration is from 12A process valve 9 and pipeline 18 emptying.
Regenerative process need be not less than 120 ℃ temperature, and preferably at least 200 ℃, the reaction of carbon monoxide of hydrogen and absorption forms methane, forms water with the oxygen reaction.Methane is easy to desorb with water and hydrogen then.Reprocessing cycle 24 hours, at regeneration period, two bed commutations replace adsorption bed with Regenerative beds.Regeneration can or be carried out every several days every 24 hours, and this depends on the capacity of container.Recovery stream becomes adverse current with absorption stream.
Also can use cryogenic purincation of the present invention system from store with liquid form and the nitrogen of transportation remove the oxygen of 0.5-1ppm and the carbon monoxide of 1-2ppm.When hypothermia distillation device was not worked, typically nitrogen was stored with liquid form, to satisfy service requirements.The standby storage liquid of groove 19 uses vaporizer 20 to be heated to room temperature, and through valve V4, pipeline 21 and valve V2 are to low temperature purifier.The product liquid of storing typically contains hydrogen seldom, because hydrogen vaporization when transportation and in liquid storage vessel has been fallen.No matter and the load of carbon monoxide is at low temperature or at room temperature all be identical, so it has determined the container dimensional of low-temperature adsorber.Therefore, the size of low temperature purifier both can be used for the purifying that present method also can be used for liquid nitrogen.
Because purifier is in low temperature, when process nitrogen during through it, the standby nitrogen that leaves purifier from bed 12A or bed 12B is cold at the very start.Heat product nitrogen if desired, then allow product nitrogen pass through valve V10 or valve V14 and pipeline 22 respectively and be sent to the electric heating glycol/water and bathe 23.Hot-fluid is sent to hay tank 25 through pipe 24.Handle in hay tank device 25 through pipeline 13 or 24 logistics, so that remove fine particle by managing 26 before emitting recovery at product.
In addition, under the equal in quality flow velocity, the volume of the evaporated liquid nitrogen of process purifier can be greater than the volume of the cryogenic nitrogen that passes through revivifier during normal running.During the vaporized nitrogen purifying, the pressure-losses by purifier is four times of the pressure-losses that observes with process steam approximately., the pressure that obtains in liquid storage vessel is quite high typically.Therefore, this pressure that has increased does not fall and can cause problem.
Fig. 1 example has illustrated particularly preferred embodiment of the present invention, and in this embodiment, the nitrogen for ultra-high purity that a part of cryogenic absorption system produces turns back to the top of low-temperature fractionating tower 7 through pipeline 28, preferably turns back to the top.This reflux operation has improved the efficient of air separation plant, has reduced the oxygen level of the nitrogen of low-temperature fractionating tower generation.Nitrogen for ultra-high purity enters evaporator overhead condenser, is used for producing refluxing.If necessary, pipeline 29 can be removed the nitrogen of the condensation of evaporator overhead condenser 31, and reclaims as ultra-pure liquid nitrogen.
Table 1 is included in the laboratory characteristic present who under 87k (183 ℃) temperature cryogenic absorption material of having identified is the carried out resulting data of working.Select the criterion of cryogenic absorption agent material to be that this sorbent material can adsorb carbon monoxide, oxygen and the hydrogen of maximum mole number with every mole metal in its low temperature adsorbent.The best low temperature sorbing material of being identified by cut-and-try work is HTC-500 TMCrosfield nickel catalyzator (businessman has bought by Chicago, Illinois Crosfield catalyzer).
Table 1
Source/sorbent material Form H/M CO/M O/M Explain
METADYNE (Elma，NY) The tungsten sponge - ＜0.01 - ＞700 ℃ of regeneration down
Union Carbide (Danbury， CT) 9%CuO-Y zeolite te - 0.23 -
Crosfield/HTC-500 TM 20％NiO/Al 2O 3 0.01 0.09 0.02
BASF(Mt.Olive，NJ)/ R-3-12 TM CuO/ZnO/Al 2O 3 - ＜0.01 - Based on 40%Cu +Load
Union Carbide/OC-112 TM 50％CuO；MnO 2/SiO 2 - ＜0.01 ＜0.01
Carus (Ottawa，IL)/ Carulite-300 TM 75％MnO 2；15％ CuO/Al 2O 3 - ＜0.01 ＜0.01 Based on 75%Mn +3Load
Degussa(Tulsa， OK)/E-221 TM 0.5％Pd/Al 2O 3 - 1.1 -
United Catalyst (Louisville， KY)/C12-4-02 TM Fe/Al 2O 3 - ＜0.01 0.01 Based on 80%Fe +2O 2Load
Engelhard (Iselin， NJ)/CR-0211 T 5/32＂ TM 18％Cr 2O 3/Al 2O 3 - ＜0.01 ＜0.01
Engelhard/Silica 2351 T 1/8＂ TM 90% silicon-dioxide/Al 2O 3 - - ＜0.01
Engelhard/Co-0138 E 1/16＂ TM 30%Co/ silicon-dioxide - 0.02 ＜0.01
Various The 5A molecular sieve - 0.04 -
In the table 1, H/M, CO/M, O/M are respectively atomic hydrogen, carbon monoxide and the oxygen mol ratios to given metal.
In another preferred embodiment of the present invention, using independently, the cryogenic absorption system for example produces nitrogen for ultra-high purity from the nitrogen of liquid nitrogen storage or liquid trailer by the nitrogen of levels of the standard.Fig. 2 has represented schema.Use cryogenic absorption of the present invention system to adsorb to come purifying to contain the nitrogen of concentration as one or more impurity of 0.1-10ppm in 1ppb or oxygen still less, hydrogen or the carbon monoxide by the low temperature gas chemistry.
Shown in Fig. 2 schema, liquid nitrogen takes out from groove 101, flows through pipeline 102, by vaporizer 103, or the valve 104 by walking the vaporizer bypass.In either case, vaporized nitrogen all remains on the temperature of 150k or is lower than the temperature of 150k, and 80-100k preferably most preferably is maintained at about the temperature of 90k.Nitrogen in the pipeline 105 stream as gas, or as liquid, enters the catalytic bed top with 1-10 gallon/time with whole prod stream, carries out flash distillation.When not using, the catalytic bed cryogenic refrigeration is kept in flash distillation.The high-purity nitrogen vapor of low temperature flows through catalytic bed 106, and in this catalytic bed, at least a impurity (oxygen, hydrogen and carbon monoxide) reaches 1ppb or lower through chemisorption.The container 107 that comprises catalytic bed has only an entrance and exit, for flowing and/or catalyst treatment usefulness.The heat insulation low temperature of keeping of container application low temperature.Container is axial.Nitrogen for ultra-high purity steam maintains low temperature, by manage 108 from then on the bed outlet at bottom emit.Nitrogen for ultra-high purity is heated to room temperature in vaporizer 109, utilize pressure-regulator 110 to regulate its pressure, and it is by particle filtration jar 111, so that eliminate any particulate matter before recovery.
Preferred nickel catalytic bed has continuous purification cryogenic nitrogen steam and reaches 30 days and need not the regenerated ability.This is preferably enough big, be enough to that purifying reached 30 days from the nitrogen of liquid nitrogen storage tank or liquid trailer and can the more not frequent recovery time at interval, for example works below the moon for 6-12.For example, for a kind of device of per hour producing 180,000 cubic feet of (CFH) nitrogen, needed catalytic amount is at least 500 pounds, but no more than 5000 pounds.
Low temperature purifier shown in Figure 2 does not have prolonged regenerative power.Can use utility appliance to carry out regenerative operation at the scene at the scene or not and make catalyst regeneration.Fig. 3 illustration devices needed and device.Make through the mixing so that in pipeline 203, produce the recovery stream of nitrogenous and about 1% (volume) hydrogen with hydrogen source logistics of pipeline 201 and valve 210, realize regenerating with this through pipeline 202 and valve 211 near about 5% nitrogen for ultra-high purity of room temperature.Recovery stream enters static mixer 204, to guarantee good mixing.Mixing tank is not indispensable for successfully carrying out this process.Recovery stream through pipe 205, enters well heater 206 then, is heated in well heater and is not less than 120 ℃, preferably at least 200 ℃.When type of thermal communication was crossed pipe 207 discharge well heaters, its entered catalyzer adsorption bed 208 through stopping valve 212, and adsorbent bed is heated by hot-fluid, discharges any material that is adsorbed.Useless recovery stream is by bed and pipe 209 emptying.
Regenerative process needs at least 120 ℃ temperature, and preferably at least 200 ℃, hydrogenous air-flow is reduced to methane with the carbon monoxide that is adsorbed, and hydrogen reduction is formed water.The mixture flow of methane and water and hydrogen is easy to then by desorb.The reprocessing cycle cycle comprises the heating and cooling operation, can from 24 hours to 2 weeks, this depends on the capacity of container.Recovery stream becomes adverse current with absorption stream.
Though the present invention with reference to some embodiment preferred have been described in detail, it will be recognized by those skilled in the art in the spirit and scope of claim, other embodiment of the present invention to be arranged.

Claims (10)

1. produce the cryochemistry adsorption method of nitrogen for ultra-high purity, this method is included in containing metal sorbent material at least a in the nitrogen that contains one or more impurity in hydrogen, oxygen or the carbon monoxide and nickeliferous, copper, palladium and the iron is contacted, and the content of producing hydrogen, oxygen and carbon monoxide is less than the nitrogen for ultra-high purity of 1ppb.
2. the process of claim 1 wherein that sorbent material contains nickel.
3. the method for claim 2, wherein sorbent material is nickel (II) oxide compound of mechanical carrier band on salic matrix.
4. the process of claim 1 wherein in the atmosphere that also is included in hydrogen and nitrogen for ultra-high purity in the regeneration that is not less than under 120 ℃ the temperature sorbent material.
5. the method for claim 4, wherein sorbent material contacts with the mixture of hydrogen and nitrogen for ultra-high purity and regenerates.
6. the process of claim 1 wherein that nitrogen takes from low-temperature fractionating tower.
7. the process of claim 1 wherein that nitrogen takes from liquid nitrogen storage.
8. the method for claim 6, wherein a part of nitrogen for ultra-high purity is incorporated into the top of low-temperature fractionating tower.
9. the method for claim 8 wherein also comprises from low-temperature fractionating tower and reclaims nitrogen for ultra-high purity.
10. the method for claim 7, wherein nitrogen with volatilization fast before sorbent material contacts.
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